Basic dye



Patented Feb. 21, 1928.

UNITED STATES PATENT OFFICE.

JEAN KERN, OF NEW YORK, N. Y., ASSIGNOB TO E. I. DU PON'I DE NEMOURS &COM- PAINT, 0F WILKINGTON, DELAWARE, A CORYOBATION OF DELAWARE.

BASIO DYE.

No Drawing.

This invention relates to printing and dyeing with basic dyes and hasfor its general object improvements in the preparation and use of suchdyes whereby fast colors are produced more expeditiously and cheaplythan heretofore.

One specific object is to provide a basic dye printing color and also amethod of using same, whereby the usual steaming process can bedispensed with.

A further specific object is to produce dyeing li uors of basic dyeswhich are capable of yeing fibers very rapidly, thereby renderingunnecessary the prolonged and repeated immersions heretofore necessaryfor good results.

A further specific object is to produce dyeing liquors of basic dyeswhich are perfectly clear solutions.

A further specific object is to produce dyeing liquors of basic dyeswhich can be used in the cold or at ordinary temperatures.

A further specific object is to provide continous printing and dyeingrocesses with basic dyes whereby'production is greatly increased andgreat economies made in capltal charges, labor and materials.

A further object is to provide basic dye printing and dyeing processesin which the consumption of tanmc acid is greatly reduced in comparisonwith the prior processes, being used substantially in the amountnecessary for the color used.

In accordance with the present invention the printing color or dyeingliquor is produced in the form of a solution with an active agent,preferably tannic acid, in suitable solvents as a water solublealiphatic acid or a mixture thereof with lycerine. The active agent iscaused to com ine with the basic dye by heating or boiling to effectmodification. The modification is preferably complete and thiscompletion is easily determined by diluting a small quantity of theliquor in water. If the modification is not completely affected, thewater is colored by the dye. If the modification is completely effected,the lake is precipitated by the water. Thereafter the-solution isdiluted by an acid solution for use as a dyeing Application filedDecember 36, 1922. Serial No. 609,105.

liquor or a thickener is incorporated to produce a printing material. Inthis manner of preparation a modified dye is produced in solution whichreadily combines with the fabrics and fast colors are produced withgreat ease.

As heretofore practised, the printing of fabrics with basic dyescomprised the steps of printing, drying and steaming that is, exposinthe fabric to the action of steam or one or one and one-half hours forthe purpose of produ cin an insoluble lake on the fibers. Therea ter thefabric was treated with antimony salt, such as tartar emetic.

The present printing process dispenses with the steaming operation, andis particularly adapted for use as a continuous procass-that is, the webof the fabric may be passed continuously throughout the process Withoutaccumulation for the purpose of steaming or the like. The printedmaterial can be completely finished inas little as five minutes. Iestimate that the output for the same plant can be increased from sevento ten times by substituting the present for the prior printingprocesses.

The great advantages of the resent invention will appear from thefoilowing'examples which are given for the purpose of illustrating theinvention.

PREPARATION or PRINTING COMPOUND. Example I (red). Mix:

Tannic so ution (containing tannic acid and lactic acid in theproportion 1:2) 48-145 Heat the above mixture for about five minutespreferably to boiling and add 567-856 parts by weight of a thickener.preferably starch containing 1092-2079 of acetic acid.

One preferred form of this example comrised 30 grams of rhodamine, 75parts of actic acid, 75 parts of water, 108 parts of glyoerinesolution,145 parts of tannic solution and 567 parts of acid starchpaste.

Ewample II (yellow).

Mix: by iiaght.

Auramine O -30 Lactic acid (50%) 25-75 10 Water 25-75 Glycerine solution(containing glycerine, formic acid (85%) and phthalic ortetrachlor-phthalic acid in the proportion 75: 30 2) 36-108 Tannicsolution (composed of tannin,water and glacial acetic acid in equalparts) 60-180 Heat to 85 C. until the formation of the modified dye iscomplete, which may be recognized by complete precipitation of color inwater upon testing, and add 532-844 parts bydweight of thickenercontaining 10-20% am Example HI (blue).

Mix: by 352a.

Setocyanine 10-30 Lactic acid 25-75 Water 25-75 Solution gl cerine(containing glycerine, ormic acid and benzoic acid in proportions 25:

10:1) 36-108 Tannic solution (composed of 3 parts of tannin to two partsof 95% formic) 50-150 This mixture is heated five minutes and 562-854parts by weight of thickener contaming 10% to 20% acid are added.

Example IV (violet).

Parts Mix: by weight.

Methyl violet 2B 10-30 Water 25-75 Lactic acid 25-75 Glycerine solution(containing glycerine, formic acid and benzoic acid in proportions 25:

10:1) 36-108 Tannic solution (composed of tanni'n, water and glacialacetic acid in equal parts) 93-279 producing darker shades usually ofdark colors iron salts may be substituted for the antimony salts. Thepresent invention is not limited to the use of antimony and iron saltsas fixing and firming mordants. Any equivalent mordants may be used forthis pur ose. The Schultz numbers of the dyes emp oyed in the examplesare:

Du Pont methylene blue BX, Schultz No. 659.

Aurainine O, Schultz No. 493.

Setocyanine, color index No. 663.

Du Pont rhodaminc GGDN, unclassified.

The resent invention also comprises the production and application ofdyeing liquors which contain a modified basic dye in solution, adaptedto deposit on the fibres with greater ease than heretofore.

The solution is produced in the manner closel analogous to theproduction of the printing compositions, but for the purpose of dyeingno thickener is added and the solutions are preferably diluted byfurther acid liquids.

The following examples of dyes are given for the purpose of illustratingthe manner in which the dyeing liquor is produced.

Ewample I (red) Parts Mix: by weight.

Rhodamine (6 extra poudre) 10-30 Lactic acid (50%) 25-75 Water 25-75Glycerine solution (containing Example 11 (yellow).

rm Mix: by weight.

Auramine O 10-30 Lactic acid (50%) 25-75 Water 25-75 Glycerine solution(containing glycerine, formic acid (85%) and phthalic ortetrachlorphthalic acidin the proportion 75:30:22) Tannic solution(composed of tannin,'\vater and glacial acetic acid in equal parts)60-180 Heat to 85 C. until the formation of the i'io lake is complete,which may be reco ized Solution glycerine (containing glycerine, formicacid, and benzoic acid 1n proportions 25 :10: 1)

Tannic solution (composed of 3 parts of tannin to two parts of p 95%formic) 50-150 This mixture is heated five minutes and diluted with10-20% acetic, formic or lact c acid.

Ewample I V (violet). Parts Mix: by weight.

Methyl violet 10-30 Water 25-75 Lactic acid 25-75 Glycerine solution(containing glycerine, formic acid and benzoic acidin roportion 25:10:1)3-108 Tannic so ution (com osed of tannin, water and g acial acetic acidin equal parts) 92-279 Heat the mixtiire to 95 C. for 10 minutes anddilute with 10-20% acetic, formic or lactic acid.

In the usual practice of dyeing with basic dyes it is usual first toimpregnate the fabric with tannic acid and antimony salt for aconsiderable time and thereafter to dye with a solution of the basiccolor in acetic acid, with repeated immersion in the dyeing liquor whichis made warmer and warmer as the o oration continues. This operationtook a out five or six hours and it was therefore practically impossibleto make the process continuous.

By using the basic coloring liquors prepared according! to the inventionand exemplified by t e foregoing examples, it is possible to dye thecloth by assing through the dye liquor once only an thereafter the dyerequires only to be fixed by a firmin or fixing bath.

The yeing process according to the invention is not, however, limited toa single immersion in the dye liquor, as repeated immersions may bemade, in some cases with different dyeing liquors. I have, however, beensuccessful in producing fast dyed fabrics of practicall all colors by asingle immersion with su equent treatment with a fixing or firmingmordant.

The present yeing process can be operated continuously an as far as I amaware it is the first continuous process of dyeing with basic dyes whichis capable of continuous operation. The fabric is fully dyed and inmarketable condition in a few minutes after the bleached fabric is fedinto the dyeing liquor.

The dyeing operation consists in the bleached fabric through the dyeingliquor, pressin between rolls to remove excess of liquor, r ing well,passing throu h a assingsolution of a xin mordant, -for examp e anantimony salt, sue as tartar emetic, washing a'nd dr ing. No preliminarypreparation of the abric with tannic acid or antimony salt is necessaryaccording to the present invention.

It will be obvious that other solvents or solvent mixtures than thosespecifically mentioned in the foregoing examples may be employed inpreparing the solution of the color and active agent. While watersoluble aliphatic acids generally may be employed for this purpose,formic, lactic and acetic acids are preferred. Similarly, whilepolyalcohols gcnerall (substances belonging to the broad class aving analiphatic hydrocarbon radical attached to more than one hydroxyl groufor instance, ethylene glycol and glycerine ma be employed in admixturewith the acids, in my preferred embodiment, I employ glycerine. If asingle solvent is employed instead of a mixture, an acid, for example,formic or lactic acid, should be selected. The use of the mixture ofglycerine, lactic acid and formic acid has been shown for illustrativepurposes in the examples simply because this mixture has been ound togive excellent results.

I have used the term tannic acid in the foregoing descri tion and in theap ended claims, and by t is term I intend to include the material soldunder this termand its recognized equivalent and also the materialfrequently referred to as tannin.

The dye compositions and processes herein described are adapted for usewith cotton, wool, silk and linen fabrics, and in fact to all fiberswhether of vegetable or animal origin.

phthalic acids. The aromatic acids are preferably incorporated with theinitial mixture as shown in the foregoing examples, while it ispreferred to use the aliphatic acids in the thickener in the case of theprinting compositions and in the diluting liquid in the case of thedyeing liquors. The amount of the aforesaid aliphatic acids should befrom 2 to 10 grams per litre of the dyeing composition, and its useaccording to the lowermost part of this range is preferred. Turkey redoil can also be used as a bright ening agent.

An important featureof the resent invention resides in the fact that t esolution of the modified dye produced according to the present inventioncan be dried or evaporated and thereafter dissolved with reproduction oftheir original dyeing properties. The volatile products can readily berecovered and used in the preparation of further batches of dyeingmaterial. The dried product is of gumlike consistency and can readily beredissolved by organic acids such as formic, acetic or lactic acids orthe like or mixtures thereof. For example 100 parts of the solid lakecan be easily dissolved in 400 parts of water containing 10 to 25% ofacid. For printing, it is necessary to add thickener to the desiredextent. This property enables the improved dyeing composition to be soldin solid form and the purchaser can immediately dissolve the same andobtain the reat advantages of my invention forthwit at the shortestnotice.

What I claim is:

1. The method of reparing a color adapted for textile printing whichcomprises producing a substantially complete solution of a basic colorand tannic acid and heating said solution substantially to boiling.

2. The method of preparing a printing composition which comprisessubstantially completely dissolving a basic dye and tannic acid in awater soluble aliphatic acid, heating and adding a thickener 3. Themethod of produciiiga textile printing color adapted to give a fixedcolor without steaming, which comprises mixing a solution of a basiccolor with tannic acid previously dissolved in an aqueous solution of anacid selected from a group consisting of formic, lactic and acetic acidsand boiling.

4. The method of producing a textile printing color adapted .to give afixed color without steaming, which comprises separately preparing asolution of a basic color and a solution of tannic acid comprisinglactic acid, mixing said solutions and boillIl 5. The method ofproducing a dye in solid form which comprises mixing a basic color withtannic acid in the presence of an aqueous solvent for the reactionmixture, said solvent comprising an acid selected from a groupconsisting of formic, acetic or lactic acids, boiling and evaporating toobtain a gumlike product.

6. The method of preparing a coloring medium which comprises mixing asolution of basic' dye with a separately prepared solution of tannicacid comprising an aqueous solution of an aliphatic acid and heatinguntil the color is substantially completely precipitated by dilutionwith an excess of water.

7. The method of preparing a coloring medium which com rises adding abasic dye to tannic acid in the presence of a solvent for both dye andacid, heating the mixture and periodlcally testing portions thereof forprecipitation with an excess of water, said heating being continueduntil the color is substantially completely precipitated by excess ofwater.

8. The method of producing a textile printing color adapted to give afixed color without steaming which comprises dissolving a basic color inan aqueous liquid comprising lactic acid, dissolving tanmc acid in anaqueous solution of an acid selected from a group consistin of lactic,acetic and formic acids, mixing the resulting solutions and heatin themixture substantially to boiling.

9. e method of producing a textile printing color adapted to give afixed color without steaming which comprises mixing a basic color withtannic acid in the presence of a solvent for both the color and tannicacid and heating to complete the reaction.

10. The method of reparing a textile printing com osition w ichcomprises preparing a so ution comprising rhodamine, lactic acid, water,lycerine, formic acid, benzoic acid and tanmc acid, boiling and adding athickener.

11. The method of reparing a textile printing composition whichcomprises mixmg substantiall 30 parts of basic dye, 75 parts lactic aci75 arts water, 108 parts of glycerine solution which comprisesglycerine, formic acid and benzoic acid in the proportions of 25: 10:1)and 145 parts of tannic acid solution (which comprises tannic acid andlactic acid in the proportions 1:2) heating for five minutes to boilingand add ing 567 arts of starch paste, with 10% acetic aci 12. The methodof preparing a dye which comprises producing a solution of a basic dyeand tannic acid together with an arcmatic acid selected from the grouconsisting of benzoic, phthalic or chloropiithalic acids and heating.

13. The method of preparing a dye which comprises dissolving a basic dyeand tannic acid with a water soluble aliphatic acid and an aromatic acidadapted to act as a brightening agent.

14. A basic dye composition adapted for textile printing withoutsteaming comprising a solution resulting from mixing a basic color withtannic acid in the presence of a solvent for the resulting reactionproduct and heating to complete the reaction.

15. A basic dye composition adapted for textile printing withoutsteaming comprising a solution resulting from mixing a basic dye andtannic acid in the presence of an aqueous solution of an aliphatic acidadapted to dissolve both dye and tannic acid and heating.

16. A basic dye composition obtainable by mixing a solution of tannicacid in an acid selected from a group consisting of lactic, acetic andformic acids'with a solution of a basic color in an acid selected fromthe same group and heating the resulting solution to boiling.

17. A basic dye composition adapted for textile printing withoutsteaming comprising a basic dye and tannic acid in chemical combinationin a solution containing a Water soluble aliphatic acid and an aromaticacid, said aromatic acid being adapted to function as a brighteningagent. v

18. A continuous process of fixing basic dyes on fabrics which comprisesheating a substantially complete solution of the dye and tannic acid soas to increase the afiinity of the dye for fabric, a plying theresulting solution to the fabric, rying the fabric and \n pawing itthrough a solution of a fixing mordant.

19. A process of fixing basic dyes on fabric, which dyes afterapplication ordinarily require steaming to effect fixation, whichcomprises modifying the dye by causing a substantially complete solutionof tannic acid to react with a substantially complete solution of thedye at a temperature not substantially below 95 C. printing the fabricwith the so modified dye, drying the printed fabric and mordanting.

20. The composition set forth in claim 16 wherein the solution of thedye comprises an aliphatic poly-alcohol.

21. A printing composition comprising the dye solution set forth inclaim 16 in admixture with a solvent and a thickener.

22. Textile material colored with the composition set forth in claim 16.

In testimony whereof I aflix my signature.

JEAN KERN.

aqueous solution of an aliphatic acid adapted to dissolve both dye andtannic acid and heating.

16. A basic dye composition obtainable by mixing a solution of tannicacid in an acid selected from a group consisting of lactic, acetic andformic acids with a solution of a basic color in an acid selected fromthe same group and heating the resulting solution to boiling.

17. A basic dye composition adapted for textile printing withoutsteaming comprising a basic dye and tannic acid in chemical combinationin a solution containing a water soluble aliphatic acid and an aromaticacid, said aromatic acid being adapted to function as a brighteningagent.

18. A continuous process of fixing basic dyes on fabrics which comprisesheating a substantially complete solution of the dye and tannic acid soas to increase the aiiinity of the dye for fabric, a plying theresulting solution to the fabric, rying the fabric and passing itthrough a solution of a fixing mordant.

19. A process of fixing basic dyes on fabric, which dyes afterapplication ordinarily require steaming to effect fixation, whichcomprises modifying the dye by causing a substantially complete solutionof tannic acid to react with a substantially complete solution of thedye at a temperature not substantially below 95 C. printing the fabricwith the so modified dye, drying the printed fabric and mordanting.

20. The composition set forth in claim 16 wherein the solution of thedye comprises an aliphatic poly-alcohol.

21. A printing composition comprising the dye solution set forth inclaim 16 in admixture with a solvent and a thickener.

22. Textile material colored with the composition set forth in claim 16.

In testimony whereof I afiix my signature.

JEAN KERN.

CERTIFICATE OF CORRECTION.

Patent No. l, 660, 167.

Granted February 21, 1928, to

JEAN KERN.

It is hereby certified that error appears in the printed; specificationof the above numbered patent requiring correction as follows:

and that the said Letters Patent should be read figures "3-108" read"36408";

Page 3, line 28, for the with this correction therein that the same mayconform to the record of the ease in the Patent Office.

' Signed and sealed this 20th day of March, A. D. 1928.

Sell.

M. J. Moore, Acting Commissioner of Patents.

CERTIFICATE OF CORRECTION.

Patent No. 1,660,167.. Granted February 21, 1928, to

JEAN KERN.

It is hereby certified that error appears in the printedspecification ofthe above numbered patent requiring correction as follows: Page 3, line28, for the figures "3-108" read "36-108"; and that the said LettersPatent should he read with this correction therein that the same mayconform to the record of the case in the Patent Office.

Signed and sealed this 20th day of March, A. D. 1928.

M. J. Moore, Acting Commissioner of Patents.

